CN109772333B - Metal surface coating catalyst directly prepared from solid and application thereof - Google Patents
Metal surface coating catalyst directly prepared from solid and application thereof Download PDFInfo
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- CN109772333B CN109772333B CN201711127273.2A CN201711127273A CN109772333B CN 109772333 B CN109772333 B CN 109772333B CN 201711127273 A CN201711127273 A CN 201711127273A CN 109772333 B CN109772333 B CN 109772333B
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Abstract
The invention relates to a metal surface coating catalyst directly prepared by solid and application thereof; the solid metal particles A and the reducible solid metal oxide B are mechanically and uniformly mixed, and are subjected to heat treatment at a certain temperature to obtain a solid mixture, wherein part of the oxide B is coated on the surface of the particles A. And separating the particles coated on the surface of A by B from the particles uniformly distributed on the surface of B in the solid mixture to obtain the metal catalyst A @ B containing the coating of B on A. The catalyst has surface B coated with monoatomic layer or polyatomic layer and excellent selectivity in catalytic hydrodeoxygenation of oxygen-containing benzene ring compounds, and the selectivity of phenolic compounds reaches over 90%. Compared with the traditional solid metal particle surface coating, the catalyst has the advantages that the coating process is simple, and the coated oxide is stable on the metal surface; moreover, the catalyst can catalyze the oxygen-containing benzene ring compounds with high selectivity to generate phenolic substances with high added values.
Description
Technical Field
The invention relates to the field of material preparation and catalysis, in particular to a metal surface coating catalyst directly prepared from a solid and application thereof. .
Background
The metal catalyst is one of the catalysts widely used in industry, but how to regulate the selectivity of the metal catalyst is always a problem to be solved urgently by researchers. Taking a nickel metal catalyst as an example, the nickel metal catalyst is a hydrogenation catalyst commonly used in industry due to its high hydrogenation activity, and compared with a noble metal hydrogenation catalyst, the nickel metal catalyst has the characteristic of low cost, which is favored by researchers. However, since the hydrogenation selectivity of metallic nickel is low, it is difficult to obtain a chemical having a high added value. Therefore, how to prepare a high-selectivity metal nickel catalyst is a major task of researchers at present, wherein an oxide-coated metal nanoparticle is one of catalysts for changing the selectivity of the metal nanoparticle, and the characteristic is that one or more layers of oxides are coated on the surface of a nano metal, so as to regulate the selectivity of the nano metal. The surface coating of the general nano metal is to uniformly disperse the nano metal in a solution by adding a surfactant, and then add a precursor of an oxide to prepare the surface-coated metal catalyst in a hydrothermal synthesis or hydrolysis mode. However, the surfactant added in the process is difficult to elute in the subsequent process, the process is complex, the prepared coated catalyst is usually unstable, and the direct preparation of the metal surface coated catalyst by a solid one-step method is not reported in documents so far. Compared with the traditional solid metal particle surface coating, the preparation process of the metal surface coating catalyst prepared directly by the solid is simple, and any surfactant is not required to be added in the midway, so that the preparation cost of the catalyst is greatly reduced; and the catalyst prepared by the method is more stable than the traditional catalyst with a coated surface, and can be used for industrial preparation on a large scale.
In the field of catalysis, with the continuous decrease of fossil fuels and the increasing demand of people for energy substances, lignin attracts attention as a substance widely existing in plants in a large amount. Nowadays, the aromatics are generally extracted from crude oil and coal, and the lignin structure is composed of aromatic high polymer, which can replace fossil fuel as the source of aromatics. In recent years, efforts to catalytically convert lignin to fuels and chemicals have gradually created a hot direction of research, with highly efficient metal catalysts being the primary subject of research.
In view of the reaction characteristics, the metal surface coated catalyst is directly prepared by a solid one-step method, the selectivity of the catalyst is changed by obtaining the metal surface coated catalyst, and chemicals with high added values are obtained with high selectivity.
Disclosure of Invention
The invention aims to directly prepare a metal surface coating catalyst by a solid one-step method, and the catalyst is used for selective hydrogenation in a hydrodeoxygenation process to obtain chemicals with high added values.
The invention discloses a supported metal catalyst directly prepared from a solid and application thereof. The method is characterized in that solid metal particles A and reducible solid metal oxides B are mechanically and uniformly mixed, and then are subjected to heat treatment at a certain temperature to obtain a solid mixture, particles coated on the surface of A by B in the solid mixture are separated from particles uniformly distributed on the surface of B by A, and the metal catalyst A @ B coated on the surface of A is obtained after separation. The surface B of the catalyst is coated by the thickness of a monoatomic layer or a polyatomic layer, and can catalyze the oxygen-containing benzene ring compounds to prepare phenolic substances with high selectivity.
The solid metal particles A comprise Fe, Co, Ni, Cu, Zn and their alloys.
The reducible solid metal oxide B includes TiO2, V2O3, Nb2O5, Ta2O5, La2O3, CeO2, MnO and mixtures thereof.
The heat treatment temperature is not lower than 200 ℃.
The gas for heat treatment is hydrogen, carbon monoxide and the mixed gas of hydrogen, carbon monoxide and inert gas.
The separation steps of the solid mixture are as follows:
(1) dispersing the solid mixture in a dispersion solvent;
(2) separating the dispersed solid catalyst;
(3) drying the separated catalyst to obtain the catalyst.
The dispersing solvent used in the separation is water, methanol, ethanol, propanol, isopropanol or their mixture.
The separation mode during separation is magnet separation.
The drying mode after the separation is vacuum drying.
The oxygen-containing benzene ring compounds comprise guaiacol, anisole, catechol, vanillin, eugenol and mixtures and isomers thereof. The present invention uses the selectivity of phenolic species to evaluate catalysts.
The metal surface coating catalyst prepared by the invention has simple preparation process and convenient operation, and can be used for the large-scale synthesis of the selective hydrodeoxygenation catalyst in industry.
The metal surface coating catalyst provided by the invention can be used for selective hydrodeoxygenation of benzene ring compounds to generate high value-added chemicals.
Drawings
FIG. 1 is an X-ray diffraction pattern of an untreated Ni catalyst and a Ni catalyst separated at different times of reducing gas treatment.
FIG. 2 is a transmission electron microscope image of nano nickel and nano nickel separated by reduction at 500 ℃ for 34 h.
FIG. 3 shows the selectivity of the catalyst to phenolic products in each example.
Detailed Description
The metal surface modification catalyst of the invention is mainly implemented as follows: in the case of metallic nickel and reducible titanium dioxide, guaiacol is used as the reaction raw material.
Example 1
At room temperature, 0.25g of untreated nano nickel is placed in a 50mL mechanical stirring batch kettle, 25mL of decane and 1mL of guaiacol are respectively added, and the reactor is sealed. Introducing nitrogen for 10 minutes, removing air in the reaction kettle, replacing the gas in the reaction kettle with hydrogen, and pressurizing to 4 MPa. And (3) placing the reaction kettle in a heating sleeve, heating to 350 ℃ for 1h, maintaining at 350 ℃ for 4h, cooling to room temperature after the reaction is finished, and releasing pressure. 0.2393g of an internal tetradecane standard was added to the reaction vessel, and 30mL of ethanol was added to dissolve the other reaction products. The liquid phase product is detected in a gas phase, and the result shows that the unprocessed nano nickel has high hydrogenation activity and poor selectivity to phenolic substances.
Example 2
Under the condition of room temperature, uniformly mixing the dried nano nickel and anatase phase titanium dioxide in a mortar according to the mass ratio of 1:1, placing the uniformly mixed catalyst in a quartz tube, introducing nitrogen, and removing air in the quartz tube. Then, 10% hydrogen-argon mixed gas is switched for reduction, the heating rate is 10 ℃/min, the temperature is heated to 500 ℃, and the temperature is maintained for 1h at 500 ℃. After the reaction is finished, nitrogen is switched to cool to room temperature, and the reduced mixed catalyst of the nano nickel and the titanium dioxide can be obtained. Dispersing the catalyst in deionized water, ultrasonically oscillating and dispersing in an ultrasonic cleaner, attracting by a magnet after dispersion, filtering out components dispersed in an aqueous solution, and adding deionized water again for ultrasonic cleaning until the solution is clear. Drying the cleaned catalyst in a vacuum drying oven at 60 ℃ overnight to prepare the nano nickel catalyst separated by reduction for 1 h. The nickel is shown as a diffraction peak of the simple substance nickel by the analysis of an X-ray diffraction pattern. 0.25g of the catalyst was placed in a 50mL mechanically stirred batch still, 25mL of decane and 1mL of guaiacol were added, respectively, and the reactor was sealed. Introducing nitrogen for 10 minutes, removing air in the reaction kettle, replacing the gas in the reaction kettle with hydrogen, and pressurizing to 4 MPa. And (3) placing the reaction kettle in a heating sleeve, heating to 350 ℃ for 1h, maintaining at 350 ℃ for 4h, cooling to room temperature after the reaction is finished, and releasing pressure. 0.2393g of an internal tetradecane standard was added to the reaction vessel, and 30mL of ethanol was added to dissolve the other reaction products. The liquid phase product is detected in a gas phase, and the result shows that the hydrogenation selectivity of the separated nano nickel is changed, and the selectivity of the phenolic substance is 95%.
Example 3
Under the condition of room temperature, uniformly mixing the dried nano nickel and anatase phase titanium dioxide in a mortar according to the mass ratio of 1:1, placing the uniformly mixed catalyst in a quartz tube, introducing nitrogen, and removing air in the quartz tube. Then, 10% hydrogen-argon mixed gas is switched for reduction, the heating rate is 10 ℃/min, the temperature is heated to 500 ℃, and the temperature is maintained for 4h at 500 ℃. After the reaction is finished, nitrogen is switched to cool to room temperature, and the reduced mixed catalyst of the nano nickel and the titanium dioxide can be obtained. Dispersing the catalyst in deionized water, ultrasonically oscillating and dispersing in an ultrasonic cleaner, attracting by a magnet after dispersion, filtering out components dispersed in an aqueous solution, and adding deionized water again for ultrasonic cleaning until the solution is clear. Drying the cleaned catalyst in a vacuum drying oven at 60 ℃ overnight to prepare the nano nickel catalyst separated by reduction for 4 h. The nickel is shown as a diffraction peak of the simple substance nickel by the analysis of an X-ray diffraction pattern. 0.25g of the catalyst was placed in a 50mL mechanically stirred batch still, 25mL of decane and 1mL of guaiacol were added, respectively, and the reactor was sealed. Introducing nitrogen for 10 minutes, removing air in the reaction kettle, replacing the gas in the reaction kettle with hydrogen, and pressurizing to 4 MPa. And (3) placing the reaction kettle in a heating sleeve, heating to 350 ℃ for 1h, maintaining at 350 ℃ for 4h, cooling to room temperature after the reaction is finished, and releasing pressure. 0.2393g of an internal tetradecane standard was added to the reaction vessel, and 30mL of ethanol was added to dissolve the other reaction products. The liquid phase product is detected in a gas phase, and the result shows that the hydrogenation selectivity of the separated nano nickel is changed, and the selectivity of phenolic substances reaches 96%.
Example 4
Under the condition of room temperature, uniformly mixing the dried nano nickel and anatase phase titanium dioxide in a mortar according to the mass ratio of 1:1, placing the uniformly mixed catalyst in a quartz tube, introducing nitrogen, and removing air in the quartz tube. Then, 10% hydrogen-argon mixed gas is switched for reduction, the heating rate is 10 ℃/min, the temperature is heated to 500 ℃, and the temperature is maintained for 8h at 500 ℃. After the reaction is finished, nitrogen is switched to cool to room temperature, and the reduced mixed catalyst of the nano nickel and the titanium dioxide can be obtained. Dispersing the catalyst in deionized water, ultrasonically oscillating and dispersing in an ultrasonic cleaner, attracting by a magnet after dispersion, filtering out components dispersed in an aqueous solution, and adding deionized water again for ultrasonic cleaning until the solution is clear. Drying the cleaned catalyst in a vacuum drying oven at 60 ℃ overnight to prepare the nano nickel catalyst separated by reduction for 8 h. The nickel is shown as a diffraction peak of the simple substance nickel by the analysis of an X-ray diffraction pattern. 0.25g of the catalyst was placed in a 50mL mechanically stirred batch still, 25mL of decane and 1mL of guaiacol were added, respectively, and the reactor was sealed. Introducing nitrogen for 10 minutes, removing air in the reaction kettle, replacing the gas in the reaction kettle with hydrogen, and pressurizing to 4 MPa. And (3) placing the reaction kettle in a heating sleeve, heating to 350 ℃ for 1h, maintaining at 350 ℃ for 4h, cooling to room temperature after the reaction is finished, and releasing pressure. 0.2393g of an internal tetradecane standard was added to the reaction vessel, and 30mL of ethanol was added to dissolve the other reaction products. The liquid phase product is detected in a gas phase, and the result shows that the hydrogenation selectivity of the separated nano nickel is changed, and the selectivity of the phenolic substance reaches 95%.
Example 5
Under the condition of room temperature, uniformly mixing the dried nano nickel and anatase phase titanium dioxide in a mortar according to the mass ratio of 1:1, placing the uniformly mixed catalyst in a quartz tube, introducing nitrogen, and removing air in the quartz tube. Then, 10% hydrogen-argon mixed gas is switched for reduction, the heating rate is 10 ℃/min, the temperature is heated to 500 ℃, and the temperature is maintained for 34h at 500 ℃. After the reaction is finished, nitrogen is switched to cool to room temperature, and the reduced mixed catalyst of the nano nickel and the titanium dioxide can be obtained. Dispersing the catalyst in deionized water, ultrasonically oscillating and dispersing in an ultrasonic cleaner, attracting by a magnet after dispersion, filtering out components dispersed in an aqueous solution, and adding deionized water again for ultrasonic cleaning until the solution is clear. Drying the cleaned catalyst in a vacuum drying oven at 60 ℃ overnight to prepare the nano nickel catalyst separated by reduction for 34 h. The nickel is shown as a diffraction peak of the simple substance nickel by the analysis of an X-ray diffraction pattern. 0.25g of the catalyst was placed in a 50mL mechanically stirred batch still, 25mL of decane and 1mL of guaiacol were added, respectively, and the reactor was sealed. Introducing nitrogen for 10 minutes, removing air in the reaction kettle, replacing the gas in the reaction kettle with hydrogen, and pressurizing to 4 MPa. And (3) placing the reaction kettle in a heating sleeve, heating to 350 ℃ for 1h, maintaining at 350 ℃ for 4h, cooling to room temperature after the reaction is finished, and releasing pressure. 0.2393g of an internal tetradecane standard was added to the reaction vessel, and 30mL of ethanol was added to dissolve the other reaction products. The liquid phase product is detected in a gas phase, and the result shows that the hydrogenation selectivity of the separated nano nickel is changed, and the selectivity of phenolic substances reaches 98%.
Claims (6)
1. A metal surface-coated catalyst directly prepared from a solid, characterized in that the catalyst is prepared by the following method: after mechanically and uniformly mixing the solid metal particles A and the reducible solid metal oxide B, carrying out heat treatment on the mixture at a certain temperature to obtain a solid mixture, separating particles coated on the surface of the solid mixture B from particles uniformly distributed on the surface of the solid mixture A, and separating to obtain a metal catalyst A @ B containing the metal catalyst coated on the surface of the solid mixture A; the surface B of the catalyst is coated by the thickness of a monoatomic layer or a polyatomic layer, and can catalyze oxygen-containing benzene ring compounds to prepare phenolic substances with high selectivity; the selected solid metal particles A are Ni; the reducible solid metal oxide (B) is selected to be TiO2(ii) a The heat treatment temperature is not lower than 200 ℃; the gas for heat treatment is hydrogen, carbon monoxide and the mixed gas of hydrogen, carbon monoxide and inert gas; the separation method used in the separation is magnet separation.
2. The metal-coated catalyst as claimed in claim 1, which is prepared directly from a solid, wherein the separation of the solid mixture is carried out as follows:
(1) dispersing the solid mixture in a dispersion solvent;
(2) separating the dispersed solid catalyst;
(3) drying the separated catalyst to obtain the catalyst.
3. The metal-coated catalyst as claimed in claim 2, wherein the dispersing solvent used for the separation is water, methanol, ethanol, propanol, isopropanol or their mixture.
4. The metal-coated catalyst as claimed in claim 2, wherein the drying method after separation is vacuum drying.
5. The solid direct-prepared metal surface-coated catalyst according to claim 1, wherein the oxygen-containing benzene ring compound comprises guaiacol, anisole, catechol, vanillin, eugenol, and mixtures and isomers thereof.
6. The use of the metal surface-coated catalyst directly prepared from a solid according to claim 1, wherein the catalyst can catalyze the preparation of phenols from the oxygen-containing benzene ring compounds with high selectivity.
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